WO2005047364A1 - Compositions de resine vinylester ou polyester non saturee pre-acceleree - Google Patents

Compositions de resine vinylester ou polyester non saturee pre-acceleree Download PDF

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Publication number
WO2005047364A1
WO2005047364A1 PCT/EP2004/011417 EP2004011417W WO2005047364A1 WO 2005047364 A1 WO2005047364 A1 WO 2005047364A1 EP 2004011417 W EP2004011417 W EP 2004011417W WO 2005047364 A1 WO2005047364 A1 WO 2005047364A1
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WO
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Prior art keywords
resin composition
resin
ascorbic acid
composition according
resins
Prior art date
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PCT/EP2004/011417
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English (en)
Inventor
Johan Franz Gradus Antonius Jansen
Ivo Ronald Kraeger
Franciscus Johannes Marie Derks
Original Assignee
Dsm Ip Assets B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
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Priority to EP04765936A priority Critical patent/EP1682601A1/fr
Publication of WO2005047364A1 publication Critical patent/WO2005047364A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters

Definitions

  • the present invention relates to pre-accelerated unsaturated polyester resin or vinyl ester resin compositions, curable with liquid peroxides.
  • the resin compositions show good curing properties and have a strongly reduced content of cobalt as compared to the state of the art pre-accelerated unsaturated polyester resin or vinyl ester resin compositions.
  • the present invention further also relates to objects and structural parts prepared from such unsaturated polyester or vinyl ester resins.
  • gel time is a very important characteristic of the curing properties.
  • the time from reaching the gel time to reaching peak temperature, and the level of the peak temperature (higher peak temperature generally results in better curing) are important.
  • gel time represents the time lapsed in the curing phase of the resin to increase in temperature from 25 °C to 35 °C. Normally this corresponds to the time the fluidity (or viscosity) of the resin is still in a range where the resin can be handled easily. In closed mould operations, for instance, this time period is very important to be known. Accordingly, the term good curing properties reflects, amongst other things, that the rein composition has suitable gel-time properties: i.e. the resin to be cured should remain sufficiently fluid for an acceptable time in the first stage of curing.
  • the gel time is rather short, i.e. in the order of some minutes to few tens of minutes.
  • the skilled man accordingly will always try to find options to achieve a minimal gel time, while retaining good mechanical properties of the ultimately cured products.
  • the skilled man also will try to find curable resin compositions having good storage stability, i.e. being stable (i.e. remain their handling properties without gellification) before being subjected to curing for at least one week after manufacture of the resin composition.
  • the state of the art unsaturated polyester or vinyl ester resin systems generally are being cured under the influence of peroxides and are pre-accelerated by the presence of metal compounds, especially cobalt salts, tertiary amines and mercaptans.
  • cobalt accelerators are the most common accelerators being used.
  • Cobalt naphthenate and cobalt octanoate are the most widely use accelerators in the resins of the state of the art.
  • In the standard unsaturated polyester and vinyl ester resins of the prior art they are usually present in an amount of from 0.1 to 10 mmol/kg.
  • pre-accelerated unsaturated polyester resin and vinyl ester resin compositions showing good curing properties and having a strongly reduced content of cobalt can be obtained by providing pre-accelerated unsaturated polyester resin or vinyl ester resin compositions, curable with a liquid peroxide, containing: a) an ascorbic acid compound, in an amount of at least 0.1 mmol per kg of primary resin system; and b) a soluble complex containing iron with oxidation state 2 or 3, not being ferrocene or a derivative of ferrocene, in an amount of at least 0.05 mmol/kg of primary resin system, while being essentially free of cobalt.
  • essentially free of cobalt means that the content of cobalt is lower than about 0.05 mmol/kg of primary resin system.
  • primary resin system as used herein is understood to mean the total weight of the resin, but excluding any fillers as may be used when applying the resin system for its intended uses.
  • the primary resin system therefore consists of the unsaturated polyester resin or vinyl ester resin, any additives present therein (except for the liquid peroxide component that is to be added shortly before the curing) for making it suitable for being cured, for instance all kinds of compounds soluble in the resin, such as initiators, accelerators, inhibitors, low-profile agents, colorants (dyes), thixotropic agents, release agents etc., as well as styrene and/or other solvents as may usually be present therein.
  • the amount of additives soluble in the resin usually may be as from 1 to 25 wt.% of the primary resin system; the amount of styrene and/or other solvent may be as large as up to 50 wt.% of the primary resin system.
  • the primary resin system however, explicitly does not include compounds not being soluble therein, such as fillers (e.g. glass or carbon fibers), talc, clay, solid pigments (such as, for instance, titanium dioxide (titanium white)), flame retardants, e.g. aluminium oxide hydrates, etc.
  • fillers e.g. glass or carbon fibers
  • talc e.g. glass or carbon fibers
  • clay e.g. glass or carbon fibers
  • solid pigments such as, for instance, titanium dioxide (titanium white)
  • flame retardants e.g. aluminium oxide hydrates, etc.
  • the unsaturated polyester resin or vinyl ester resin may be any such resin as is known to the skilled man. Examples thereof can be found in the aforementioned review article by M.
  • Ortho resins are based on phthalic anhydride, maleic anhydride, or fumaric acid and glycols, such as 1 ,2-propylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol or hydrogenated bisphenol-A. Commonly the ones derived from 1 ,2-propylene glycol are used in combination with a reactive diluent such as styrene.
  • Isoresins these are prepared from isophtalic acid, maleic anhydride or fumaric acid, and glycols. These resins may contain higher proportions of reactive diluent than the ortho resins.
  • Bisphenol-A-fumarates these are based on ethoxylated bisphenol-A and fumaric acid.
  • Chlorendics are resins prepared from chlorine/bromine containing anhydrides or phenols in the preparation of the UP resins.
  • Vinyl ester resins these are resins, which are mostly used because of their hydrolytic resistance and excellent mechanical properties, are having unsaturated sites only in the terminal position, introduced by reaction of epoxy resins (e.g. diglycidyl ether of bisphenol-A, epoxies of the phenol-novolac type, or epoxies based on tetrabromobisphenol-A) with (meth)acrylic acid. Instead of (meth)acrylic acid also (meth)acrylamide may be used.
  • epoxy resins e.g. diglycidyl ether of bisphenol-A, epoxies of the phenol-novolac type, or epoxies based on tetrabromobisphenol-A
  • epoxy resins e.g. diglycidyl ether of bisphenol-A, epoxies of
  • the DCPD-resins can either be obtained by modification of any of the above types of resins by Diels-Alder reaction with cyclopentadiene, or by first reacting maleic acid with dicyclopentadiene, followed by resin manufacture as shown above. All of these resins, as can suitably used in the context of the present invention, may be modified according to methods known to the skilled man, e.g. for achieving lower acid number, hydroxyl number or anhydride number, or for becoming more flexible due to insertion of flexible units in the backbone, etc. Of course, also other reactive groups curable by reaction with peroxides may be present in the resins, for instance reactive groups derived from itaconic acid, citraconic acid and allylic groups, etc.
  • the pre-accelerated unsaturated polyester resin or vinyl ester resin compositions are containing an ascorbic acid compound, in a certain amount (at least 0.1 mmol per kg of primary resin system), a soluble complex containing iron with oxidation state 2 or 3 (not being ferrocene or a derivative of ferrocene; at least 0.05 mmol per kg of primary resin system), while being essentially free of cobalt.
  • the amounts of and molar ratio between the ascorbic acid compound and the soluble complex can be chosen within wide ranges.
  • the soluble complex for instance in the range of 100 mmol per kg of primary resin (or even higher) do not bring any further advantage (and even may influence the color of the resin composition negatively).
  • the molar ratio between the ascorbic acid compound and the soluble complex can suitably be chosen in the range of from 20:1 to 1:20, most preferably in the range of from 10:1 to 1:10.
  • the inventors surprisingly have found that such pre- accelerated resin compositions, being essentially free of cobalt, have excellent curing properties in curing with liquid peroxides. If the content of the ascorbic acid compound is lower than that of the lower limit of 0.1 mmol per kg of primary resin indicated, then the effect on the curing properties is too small.
  • the amount of the ascorbic acid compound, in combination with a (too) high amount of soluble complex is too high, than the combination of ascorbic acid compound and soluble complex starts to act as a softening agent and curing properties of the resin again will be poor, even though curing might become very fast.
  • the skilled man will easily be capable of finding suitable ranges of the required content of ascorbic acid compound and soluble complex. It is remarkable that excellent results in curing with liquid peroxides can be obtained in resin compositions essentially free of cobalt and already at very low levels of the ascorbic acid and/or iron compound used.
  • the ascorbic acid compound is present in the resin compositions according to the invention in an amount of from 0.1 to 60 mmol per kg of primary resin system, most preferably in the range of from 0.5 to 20 mmol per kg.
  • the ascorbic acid compound as used in the present invention can suitably be chosen from the group of ascorbic acid, ascorbic acid salts, ascorbic acid esters and other derivatives of ascorbic acid.
  • the ascorbic acid salts for instance, can be its salts with alkali or alkaline earth metals, ammonia and or amine compounds.
  • the ascorbic acid esters most preferably, are chosen from the group of C ⁇ -12 alkyl or alkenyl esters, and also may contain aromatic or (hetero)cyclic groups.
  • ascorbic acid for instance ascorbic acid amide or N-substituted derivatives thereof, can also be used.
  • the ascorbic acid compound is ascorbic acid, an ascorbic acid alkali salt or a C ⁇ -12 alkyl ester of ascorbic acid.
  • mixtures of acorbic acid compounds can be used.
  • the soluble complexes to be used can be chosen from the group of iron salts and complexes, but will not be ferrocene or a derivative of ferrocene.
  • the valence of the iron atom in these compounds is 2 or 3. It is assumed that the effectiveness of the soluble complexes in the present invention is due to the possible transition between these valence states.
  • the soluble complex is an iron salt that is soluble in the primary resin.
  • the soluble complex is most preferably used in combination with a solvent that ensures the proper solution of the soluble complex and/or of the ascorbic acid compound in the primary resin system.
  • the valence of the iron in the soluble complex as is used in the context of the present invention preferably will be such that the iron in the soluble complex resin system will be capable of undergoing transition from Fe" to Fe'", and vice versa.
  • the iron in the soluble complex has the valence state of Fe" when the iron compound is being added to the primary resin.
  • the soluble complexes used most suitably will be organo- iron compounds.
  • the complexes also can be formed in situ in the primary resin, for instance from reaction of an inorganic iron compound (e.g. a salt like FeCI 2 or FeCI 3 ) with an organic compound while forming HCI.
  • an inorganic iron compound e.g. a salt like FeCI 2 or FeCI 3
  • suitable iron compounds taking into account considerations as to required solubility in the primary resin, resistance against hydrolysis, etc.
  • Suitable solvents for ensuring the dissolution of the complex and/or of the ascorbic acid compound in the primary resin can be chosen from the group consisting of, but not limited to, C 5-16 hydrocarbons, that may be aliphatic, or ethylenically unsaturated, or containing aromatic groups; C 1-8 alkyl esters derived from C 4-20 alkyl and/or alkenyl carboxylic acids; C 1-12 alcohols; C 1-16 alkyl phosphates; and substituted lactams.
  • Suitable reactive solvents are styrene, (meth)acrylates, and N-vinyl pyrrolidone or N-vinyl caprolactam.
  • the content of cobalt is extremely reduced as compared with standard curable resin systems: the resin compositions according to the invention are essentially free of cobalt.
  • the content of cobalt is lower than about 0.05 mmol/kg of primary resin system. It is to be noticed here, that the present inventors have observed that unsaturated polyester and vinyl ester resins containing cobalt as a pre-accelerator for the curing show poor stability upon storage in case they also contain ascorbic acid.
  • the cobalt- accelerated resin often already within one day is gellified and becomes difficult to handle in curing. It is particularly advantageous if the soluble complex is present in an amount of from 0.05 to 50 mmol per kg of primary resin system, preferably of from 0.1 to 20 mmol per kg.
  • the unsaturated polyester resins and vinyl ester resins as are being used in the context of the present invention may be any type of such resins, but preferably are chosen from the group of DCPD-resins, iso-phthalic resins, ortho-phtalic resins and vinyl ester resins. More detailed examples of resins belonging to such groups of resins have been shown in the foregoing part of the specification.
  • the present invention also relates to all such objects or structural parts as are being obtained when curing the unsaturated polyester or vinyl ester resin compositions according to the invention. These objects and structural parts have excellent mechanical properties. These resins all can be cured by means of radical curing. Most advantageously, the curing is being initiated with a liquid peroxide. Of course, in addition to the peroxide further accelerators (of course, because the resins should be essentially free of cobalt, cobalt is not included in such list of accelerators) can be applied. Although in principle all peroxides known to the skilled man for being used in curing of unsaturated polyester resins and vinyl ester resins can be used, including organic and inorganic peroxides, whether solid or liquid; liquid peroxides are being preferred.
  • hydrogen peroxide may be applied.
  • suitable peroxides in general are, for instance, peroxy carbonates (of the formula - OC(O)O-), peroxyesters (of the formula -C(O)OO-), diacylperoxides (of the formula - C(O)OOC(O)-), dialkylperoxides (of the formula -OO-), etc. They can also be oligomeric or polymeric in nature.
  • An extensive series of examples of suitable peroxides can be found, for instance, in US 2002/0091214-A1 , paragraph [0018]. The skilled man can easily obtain information about the peroxides and the precautions to be taken in handling the peroxides in the instructions as given by the peroxide producers.
  • the liquid peroxide is chosen from the group of organic peroxides and hydrogen peroxide.
  • suitable liquid organic peroxides are: tertiary alkyl hydroperoxides (such as, for instance, t-butyl hydroperoxide), and other hydroperoxides (such as, for instance, cumene hydroperoxide), peroxyesters or peracids (such as, for instance, t-butyl peresters, peracetates, lauryl peroxide, and also including (di) peroxyesters), perethers (such as, for instance, peroxy diethyl ether), perketones (such as, for instance, methyl ethyl ketone peroxide, acetylacetone peroxide).
  • tertiary alkyl hydroperoxides such as, for instance, t-butyl hydroperoxide
  • other hydroperoxides such as, for instance, cumene hydroperoxide
  • peroxyesters or peracids such
  • the organic peroxides used as curing agent are tertiary peresters or tertiary hydroperoxides, i.e. peroxy compounds having tertiary carbon atoms directly united to a -O-O-acyl or -OOH group.
  • tertiary peresters or tertiary hydroperoxides i.e. peroxy compounds having tertiary carbon atoms directly united to a -O-O-acyl or -OOH group.
  • mixtures of these peroxides with other peroxides may be used in the context of the present invention.
  • the peroxides may also be mixed peroxides, i.e. peroxides containing any two of different peroxygen- bearing moieties in one molecule).
  • the peroxide is a liquid peroxide.
  • the peroxide is selected from the group of perethers and perketones.
  • the peroxide being most preferred in terms of handling properties and economics is methyl ethyl ketone peroxide (MEK peroxide).
  • MEK peroxide methyl ethyl ketone peroxide
  • the resins according to the invention also may contain an inhibitor. Inhibitors are compounds that prevent initiation of the curing reactions in the resin during storage of the resin. Especially the inhibitors increase the pot-life (i.e. shelf-life) of the resin.
  • inhibitors that are most preferred to be used are preferably chosen from the group of phenolic inhibitors, for instance t-butylcatechol; N-oxyl free radical inhibitors, for instance hydroxytempo (i.e. 2,2,6,6-tetramethyl-4-hydroxy-piperidine-N-oxyl), and carboxyproxyl (i.e. 3- carboxy-2,2,5,5-tetramethyl-1-piperidinyl-oxy); or phenothiazine.
  • phenolic inhibitors for instance t-butylcatechol
  • N-oxyl free radical inhibitors for instance hydroxytempo (i.e. 2,2,6,6-tetramethyl-4-hydroxy-piperidine-N-oxyl), and carboxyproxyl (i.e. 3- carboxy-2,2,5,5-tetramethyl-1-piperidinyl-oxy)
  • phenothiazine phenothiazine.
  • compounds derived from other metals with the exception of metal oxides (as they are considered to be iner
  • Such other metal compounds preferably organometal compounds, in particular such compounds containing copper, nickel, vanadium or manganese, and thereby can be used to lower the (environmentally undesirable) cobalt content of the resins.
  • various solvents are particularly suitable.
  • Such solvents already also may be present in the primary resin before the complex and/or ascorbic acid compound are being added thereto.
  • the unsaturated polyester resins used in the present invention may contain solvents.
  • the solvents either can be inert towards the resin system during curing, or may be reactive therewith. Reactive solvents are most preferred.
  • the unsaturated polyester resin or vinyl ester resin compositions according to the invention contains at least 5 wt.% of a reactive solvent.
  • solvent or combination of solvents
  • the skilled man easily can find out which solvent (or combination of solvents), in combination with the choice of soluble complex, ascorbic acid compound and amounts thereof, leads to good results in terms of curing properties of the resin compositions according to the invention.
  • the unsaturated polyester resins and vinyl ester resins according to the present invention can be applied in all applications as are usual for such types of resins.
  • the unsaturated polyester resins and vinyl ester resins according to the present invention can be applied are also marine applications, chemical anchoring, roofing, construction, relining, pipes & tanks, flooring, windmill blades, etc. That is to say, the resins according to the invention can be used in all known uses of unsaturated polyester resins and vinyl ester resins.
  • the gel time was determined as:
  • each of the Examples clearly shows the good curing properties of the resins according to the invention. Moreover, it can be seen, that gel time and peak time can be controlled in a proper way, according to the desired curing properties for the resin, by proper choice of the amounts of iron compound and ascorbic acid compound. This offers excellent opportunities in fine-tuning of the curing behavior of unsaturated polyester and vinyl ester resins.
  • the Comparative Examples A-N presented below, respectively show the level of gel time usual for cobalt accelerated resins (Comp. Ex. A) can be easily reached, or even outperformed (Comp. Ex. N) by the resins according to the invention; the negative effect as to gel times in case of addition of solely ascorbic acid (Comp. Ex.
  • Comparative Examples A-M were carried out similar to Example 1 , but for the changes as shown in Table 1 below.
  • Comparative Example N was carried out similar to Example 3, but for the changes as shown below.
  • the results of the comparative Examples are shown in Table 2.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne des compositions de résine vinylester ou polyester non saturée pré-accélérée, durcissables avec des peroxydes liquides. Ils contiennent (a) un composé d'acide ascorbique, et (b) un complexe soluble comprenant du fer à état d'oxydation 2 ou 3, n'étant ni du ferrocène ni un dérivé de ferrocène, et étant sensiblement dépourvu de cobalt. Le composé d'acide ascorbique et le complexe soluble sont chacun présents en quantité, respectivement de 0,1 mmol et au moins 0,05 mmol par kg de système de résine primaire. Ces compositions de résine présentent de bonnes propriétés de durcissement et possèdent une teneur fortement réduite en cobalt par rapport à l'état des compositions de résine vinylester ou polyester non saturée pré-accélérée de l'art antérieur. L'invention concerne enfin des objets et des parties structurelles préparés à partir de ces résines vinylester ou polyester non saturées.
PCT/EP2004/011417 2003-10-31 2004-10-06 Compositions de resine vinylester ou polyester non saturee pre-acceleree WO2005047364A1 (fr)

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Application Number Priority Date Filing Date Title
EP04765936A EP1682601A1 (fr) 2003-10-31 2004-10-06 Compositions de resine vinylester ou polyester non saturee pre-acceleree

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EP03078430.0 2003-10-31
EP03078430 2003-10-31

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006128816A1 (fr) * 2005-05-31 2006-12-07 Akzo Nobel N.V. Solution d'accelerateur stable au stockage
WO2008003492A1 (fr) * 2006-07-06 2008-01-10 Dsm Ip Assets B.V. Compositions de résine de polyester insaturé ou de résine d'ester vinylique
JP2015083680A (ja) * 2007-04-02 2015-04-30 アクゾ ノーベル ナムローゼ フェンノートシャップＡｋｚｏ Ｎｏｂｅｌ Ｎ．Ｖ． 促進剤溶液
US9187616B2 (en) 2012-10-29 2015-11-17 Ashland Licensing And Intellectual Property Llc Resin compositions
US9434814B2 (en) 2006-07-06 2016-09-06 Dsm Ip Assets B.V. Unsaturated polyester resin compositions

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1029006A (en) * 1963-07-12 1966-05-11 Konink Ind Mij Noury Novel composition for the acceleration of copolymerisation of polyesters
US5464885A (en) * 1994-04-04 1995-11-07 The Glidden Company Low VOC, aqueous dispersed, epoxy-ester acrylic graft coatings

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1029006A (en) * 1963-07-12 1966-05-11 Konink Ind Mij Noury Novel composition for the acceleration of copolymerisation of polyesters
US5464885A (en) * 1994-04-04 1995-11-07 The Glidden Company Low VOC, aqueous dispersed, epoxy-ester acrylic graft coatings

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006128816A1 (fr) * 2005-05-31 2006-12-07 Akzo Nobel N.V. Solution d'accelerateur stable au stockage
JP2008542488A (ja) * 2005-05-31 2008-11-27 アクゾ ノーベル ナムローゼ フェンノートシャップ 貯蔵安定性のある促進剤溶液
CN101184781B (zh) * 2005-05-31 2010-10-13 阿克佐诺贝尔股份有限公司 储存稳定的促进剂溶液
US8268189B2 (en) 2005-05-31 2012-09-18 Akzo Nobel N.V. Storage-stable accelerator solution
JP2014088555A (ja) * 2005-05-31 2014-05-15 Akzo Nobel Nv 貯蔵安定性のある促進剤溶液
WO2008003492A1 (fr) * 2006-07-06 2008-01-10 Dsm Ip Assets B.V. Compositions de résine de polyester insaturé ou de résine d'ester vinylique
US8039559B2 (en) 2006-07-06 2011-10-18 Dsm Ip Assets B.V. Unsaturated polyester resin or vinyl ester resin compositions
CN101484516B (zh) * 2006-07-06 2012-07-04 帝斯曼知识产权资产管理有限公司 不饱和聚酯树脂或乙烯基酯树脂组合物
US9434814B2 (en) 2006-07-06 2016-09-06 Dsm Ip Assets B.V. Unsaturated polyester resin compositions
JP2015083680A (ja) * 2007-04-02 2015-04-30 アクゾ ノーベル ナムローゼ フェンノートシャップＡｋｚｏ Ｎｏｂｅｌ Ｎ．Ｖ． 促進剤溶液
US9187616B2 (en) 2012-10-29 2015-11-17 Ashland Licensing And Intellectual Property Llc Resin compositions

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